Diarylsulphone derivatives



rivatives to a process of manufacturing the pounds are not suitable for injection purposes,

forming activity of which sometimes is reduced:

-water,sothattheycaribe iniectedonlyinsus- Patented 29.1942 2,297,024

" UNITED Sms. PATENT v I. nuarasurr a dgnmvsms no Drawing. Application Is 11, 1989, Serial.

No. 214,228. In Germany 20. 1988 w g "Claims. (CLZCHO'IJ) I This invention relates to idiplicnylsulphone deselected from the group consisting of the radicals of aliphatic po hydrosy comppunds. and of allphatic radicals and aromatic radicals of the henzone and naphthalene series which aliphatic and aromatic radicals contain-an acid group. In accordance with the present invention the aforedescribed compounds can be prepared. for instance, when reacting di-isocyanates, di-ureae chlorides, di-urethanes, di-carboxylic acid asides, di-isothiocyanates, di-cyanamlno compounds, di-

.dithiocarbamic acid ester or di-isothiourea ether derivatives of diphenylsulphone containing the i said groups in the iand 4'-positions or of its nuclear substitution products with organic compounds containing apart from an amino group in the least a group rendering the products soluble in water, for instance a carboxylic acid, sulphonicacid or sulphinic acid group or some aliphatically. bound hydroxyl groups. Thus, for instance.

aminoalkyle or aminoarylalkylcarbonlic acids.

such as glycocoll and aminophenylacetic acid. aminoalkylsulphonic acids, such as taurin, aminoaryl-carboxylic acids, -sulphonic acids or -sulv poses andhaving a high activity .on'streptococci phinic acids, as for instance aminobenzenecarinfections by the manufacture of compounds boxylic acids. aminobenzenesulphonic acids. which contain in the 4- and 4'-positions bound aminonaphthalenesulphonic acids,aminobenzeneby carbamide, th'locarbamide or guanidine groups suiphinic acids. aminoquinolinesuiphonic acids or organic radicals", bearing on their part, if desired nuclear substitution products of these compounds in the form of the salts with bases, groups renderor amino derivatives of polyvalent alcohols may in}: the products soluble in water with neutral be used. Vice-verse the reaction may also be reaction. The diphenylsulphone radical may carried out by reacting isocyanates,ureachlorides, bear further 'substituents, such as free or closed urethanes, carboxylic acid asides, isothiocyanates. hydroxyl-y or amino-groups, alkyl-, nitro or halodithiocarbamic acid esters, cyanamino compounds gen-groups. The organic radicals. substituted by or isothiourea ethers of organic'compounds. consroupsrendering the products soluble in water taining the radicals rendering the products soluble 'maybe aliphatic, aromatic and/or heterocyclic in water of the above described kind, with 4.4'-diradicals. Carboxylic acid-, sulphonic acid-- or .aminodiphenylsulphone or its nuclear substitusulphinic acid groups or some-hydroxyl groups tion products. aliphaticaliy bound, such as the polyhydroxyl The process may also be performed by convertcompounds derived from sugars,may be used as 40 ing into the ,above described diphenylsulphone ,solubilizing groups. The aforenamed. compounds compounds derivatives of the diphenylsulphides preferably are used in the form of their'salts with or diphenylsulphoxideswhich'may be substituted inorganic or organic bases for injection purposes. and which contain in the 4- and 4'-positions.

' For this purpose, for instance. the sodium-, ambound by carbamido, thiocarbamido or guanidine monium-, calcium-salts or the salts with digroups, organic radicals which on their part are ethylamine, ethanolamine, diethanolamine, pisubstituted by groups rendering th product. peridlne. ethylc ediamine. plpera l c and t e like soluble in water with neutral reaction, by means y und. The new'compounds have proved of oxidizing agents such as hydrogenperoxide as being very stable. The compounds containing and permanganate. urea groups have, for instance, the formula OFFICE same.

It is known that the 4.4'-diaminodiphenylsulphone and certain derivatives thereof have a 5 favorable influence on the streptococci infections of the warm-blooded individuals. These comsince the mineral acid salts of the 4.4'-diaminor diphenylsulphone because of a low basicity of the 10 base react acid to congo and, therefore, cause necrosis upon subcutaneous iniectiouu Besides the baseitself causes a strong formation of methaemoglobin. By acylation of the aromatic amino groups derivatives of the 4.4' -diaminodiphenyil5 sulphone were obtained. the 'methaemoglobin but these compounds are practically insoluble inpcnsion. g g I According to the present invention colorless,

readily soluble and neutraliy reacting products can be obtained being suitable for injection pur- The new compounds canalso be prepared by iz-ms-ccunt- Dao|# -NIr-oo-mai-ia P unds with a group rendering the products exposing simultaneously 4.4-diamin'odiphenyl- I sulphone derivatives and organic amino comwherein R and Bi stand for a radical rendering soluble in water to the action of phosgene, thicthe products soluble in water which radical is Phquene or to their equivalents which are suitoratetlon the water-bath.

able for the formation of urea or thiourea compounds respectively, such as urea. thiourea, carbondisulphide, dialkylcarbonates and diarylcan and are convertible into carboxylic-, sulphonic-,

sulphinice or aliphatic hydroxyl groups. For this purpose carboxylic acid-esters, -amides or -nitriles, sulphonic acid ester, sulphinic acid esters or acyl derivatives of aliphatic polyhydroxy compounds may be saponified, or products containing groups of lower oxidation than the carboxylic acid, sulphonicorsulphinic acid group, such as methyl-, aldehydeor mercapto-groups are oxidized to the carboxylic acid-, sulphonic acidor sulphinic acid compounds.

,The invention is illustrated by the following examples without being restricted thereto:

Example 1 36.2 grams of -amino-1.3-benzenedicarboxylic acid are dissolved in 200 ccs. of 2-normal sodium hydroxide solution. Thereupon a solution of grams of diphenylsulphone4.4'-di-isocyanate in 300 ccs. of acetone is slowly added drop by drop at a temperature of C. during 2 hours. The reaction mixture-is subsequently stirred at 45 C. for 3 hours, filtered and the acetone is evap- The remaining aqueous solution is filtered once again and the bis [N' (3' .5 dicarboxyphenyl) carbamido N- phenylAJ-sulphone, being readily soluble in sodium hydroxideand sodium carbonate solutions, is obtained from the filtrate by means of dilute hydrochloric acid.

13.7 grams of anthranilic acid are treated in phone-4.4'-di-isocyanate and the bis-[N'-(2- carboxyphenyl carbamido N phenyl 4 sul at 149 C. crystallizes from the concentrated solution in the cold.

Example 2 27.4 grams of para-aminobenzoic acid are dis, solved in 250 cos. of acetone. A solution of 30 grams of dipheny1sulphone-4.4'-di-isocyanate in 300 ccs. of acetone is slowly dropped in while stir-- ring at a temperature of 45 C.

After 3 hours stirring at 45 C. the solution is filtered from some undissolved substance present and the fil trate is concentrated; thereupon 54 grams of bis-IN'- (4'-carboxyphenyl) -carbamido-N-phenble in the cold in dilute sodium hydroxide and sodium carbonate solutions.

' the same manner with 15 grams of diphenylsulyl-4] -sulphone crystallize. This product is solu Ezampx' 3 20.2 grams of a 90.5% sodium sulphanilate are dissolved in .100 cos. of water. A solution'of 15 grams of diphenylsulphon'e-4.4'-di-isocyanate in 150- ccs. of acetone is added drop by drop while stirring=at 45 C.: After half an hour's stirring at 45 C. the reaction solution is filtered and the acetone is evaporated. The remaining aqueous solution yields after the addition of sodium chloride the di-sodium salt, being readily soluble in water with neutral reaction, of the bis-[N'-(4'- phenylsulphonic acid) -carbamido-N-phenyl-4lsulphone.

When dissolving 29.1 grams of the acid potassium salt of the aniline-3.5-disulphonic acid in cos. of normal potassium hydroxide solution and when adding as described above 15 grams of diphenysulphone-4.4'-disisocyanate in acetone, 37.5 grams of tetrapotassium salt of the bis- [N'- (3'.5' phenyldisulphonic acid) carbamido N- phenyl-4l-sulphone being readily soluble. in water are obtained from the remaining aqueous solution by the addition of potassium chloride.

Example 4 V 25.4 grams of sodium 1-naphthylamine-4-sulphonate are dissolved in 100 ccs. of water. A solution of 15 grams of diphenylsulphone-4.4- di-isocyanate in cos. of acetone are added drop by drop while stirring at 45 -C. After 2 hours stirring at 45-50 C. the solution is freed from some undissolved substance present'by filtration with suction and the acetone is evaporated. 31 grams of di-scdium salt of the bis- [N'- (4'-naphthalenesulphonic acid) -carbamido- N-phenylil-sulphone are obtained from the remaining aqueous solution after the addition of sodium chloride.

In an analogous manner the tetrasodium salt of the his [N' (4'.8' naphthalenedisulphonic acid) -carbamido N phenyl-4] -sulphone being readily soluble in water with neutral reaction is obtained from 69.4 grams of 1-naphthylamine- 4.8-disulphonic acid sodium and 30 grams of diphenylsulphone-4,4'-di-isocyanate; the tetrasodium salt of the bis-[N'-(3'.6'-naphthalenedissulphonic acid) -carbamido N phenyl-4l-sulphone are obtained from 65 grams of the sodium Example 5 37.8 grams of 1-amino-3-phenol-4-sulphonic acid are dissolved in 100 ccs. of 2-n0rmal sodium hydroxide solution. A solution of 30 grams of diphenylsulphone-4.4'-di1isocyanate in 300 ccs. of acetone are added drop by drop while stirring at a temperature of 45 C. After 3 hours stirring the reaction solution is filtered, the acetone evaporated and the remaining aqueous solution poured into a 35% sodium chloride solution while stirring, whereupon the disodium salt of the bis- [IV-(3' hydroxyphenyl 4' sulphonic acid) -carbamido-N-phenyl-4l-mlphone precipitates.

reaction.

trample 43.0 grams or -1-. 4-phenylenediamine-2.6-disulphonic acid are dissolved in 200 ccs. oi 2-normal sodium hydroxide solution. A solution 30 grams of diphenylsulphone-4.4-di-isocyanate in 300 ccs. 'of acetone is added drop by drop at 45 C. while stirring. After 3 hours heating at 45 C. the reaction mixture is filtered, the acetone is evaporated and the aqueous solution acidified with dilute hydrochloric acid, whereupon the disodium salt of bis-[N-(4'-aminophenyl-- 3.5'-disulphonicacid) -carbamido-N-phenyl-4lsulphone precipitates.

' r Example 7 A solution oi 25.2 grams of diphenylsu lphone- 4.4'-di-isocyanate in 200 c'cs. of acetone is added drop by drop to a solution oi! 26.3 grams of paraaminobenzene-sulphinic acid in 168 ccs. of normal sodium-hydroxide solution at a temperature of 45 C. After 2 hours stirring at 50 C. the acetone is evaporated and the 'remainingaqueous It is soluble in cold water with neutral solution is acidified with dilute hydrochloric acid, I

whereupon the bis- [N' (phenyl 4' sulphinic acid) carbamido phenyl 4l-sulphone precipitates.

Example 8 cipitated from the remaining aqueous solution by means of dilute .hydrochloric acid.

Example 9 A solution of 15 grams of diphenylsulphone- 4.4'-di-isocyanate in 200 ccs. of acetone is added drop by drop to a solution of 18.1 grams of dglucamine in 250 ccs. of water at a temperature of 50 C. during two hours while stirring. After 2 hours stirring at 50 C. the acetone is evaporated and the remaining aqueous solution is re-- moved under reduced pressure. Theremaining ido-N-phenyl- 4l -sulphone when softly heated.

Example 1.0

23 grams of bis-[N'-(6'-carbomethoxy-naphthyl-2') -carbamido N phenyl-4l-sul'phone are boiled with 150 ccs. of alcohol. 40 ccs. 01 sodium hydroxide solution (33%) and cos. of water dissolves in water ior 1 minute under reflux. A clear solution is obtained, which is poured into dilute hydrochloric acid while stirring. The corresponding carboxylic acid precipitates thereupon. 17.7

grams of the acid melting above 300 C. are obtained after filtration with suction, washing with water and drying at 100 C. The acid is readily soluble in warm sodium carbonate solution.

The starting material is 'obtained in the following manner: A suspension oi 98.5 grams of 2-naphthylamino-6-carboxylic acid methyl ester melting at 160-161" C. in 1500 ccs. 0f ortholatter one is heated to 110 C. and hydrogen chloride is introduced for Shours whereupon the hydrochloric salt is formed. Subsequently phosgene is introduced into the mixture at 170-480 C. for 12 hours until the hydrochloric salt has dissolved. After concentration about grams or the naphthyl-(2)-isocyanate 0 carboxylic acid-methylester distil under 2 mms. pressure at solidifies to crystals P1810? 183 0. The distillate ing at 123". C. v

24.8 grams of 4.4'-diaminodiphenylsulphone and 45.4 grams '0! naphthyl-(2)-isocyanate-0- 'carboxyllc acid methylester are'boiled under vire-- flux in 400 cos. of acetone for 2 hours. The

bis- [N'- (6'-carbomethoxy-naphthyl-2') -carbamido-N-phenyl-4l -sulphone obtained is filtered with suction in the cold, washed with ether and dried at 100 C. 63 grams meltingat-230-240 C. (with decomposition) are obtained.

The same condensation product, can be at...

tained when boiling 11.2 grams of diphenylsulphone-4.4'-di-isocyanate and 15 grams oi 2- naphthylamine-G-carboxylic acid methylester in 250 ccs. of acetone under reflux for 2 hours. The condensation product which has separated is flltered with suction, washed with acetone and ether and dried at 100 C. 23 grams 0! the con densation product are obtained melting some- I what lower than in the above described case.

' Example 11 15 grams oi bis-[N'-(3'-carbomethoxy-naphthyl-2') -carbamido N phenyl-4] -sulphone are saponifled with alcoholic sodium tion 10%) by short boiling, the so formed preclpitated 'v with hydrochloric acid, washed with water and dried at 100 C. 12 grams melting at a temperature above 300 C. are obtained.

The starting material is'obtained in the following manner;

15 grams of diphenylsulphone-4.4-di-isocya-- hate and 20.1 grams or 2-naphthyl-amine-3-carboxylic acid methylester (obtained. when boiling 2-naphthylamine-3-carboxylic acid with methylalcohol in the presence of concentrated sulphuric acid, yellow powder melting at 99-100" C.) are boiled under reflux in 250 cos. of acetone for 12 hours. The clear acetone solution is concentrated and the condensation product precipitated after cooling is filtered with suction, washed with ether and dried at 100 C. 15.5 grams melting at 181 C. (with decomposition) are obtained.

Example 12 isocyanate are boiled under reflux in 250 ccs.

of acetone for 12 hours. The clear acetone solution is concentrated, the condensation product precipitated is filteredwith suction; washed with ether and dried at 100 C. 17.5 grains are obtained melting at 164." C. (with decomposition).

The same product is obtained when boiling in 250 ccs. on acetone under reflux'tor 12 hours 12.4 grams 0! 4.4'-diaminodiphenylsulphone and dichlorobenzene is heated in an oil bath, which 19.1 grams of para-phenyliso-cyanateb droxide solu-' tion) are obtained.

uct melting at 264265 suction. washed with ether and dried at 100 C.-

at 189 C. are thus obtained.

15.5 grams melting at 166 C. (with decomposi- 7 tion) are obtained.

Example 13 25 grams of bis-[N'-(3'.5'-di-carbomethoxyphenyl) -carbamido N- phenyl-4l-sulphone are saponified with'alcoholie sodium hydroxide solution The acid obtained after acidification (21 grams) decomposes on heating at The starting material 'is obtained as sfollowsz 15 grams oi diphenylsulphone-4.4-di-isocyanate and 20.9 grams of 1-amino-benzene-3.5 -dicarboxylic acid methylester are boiled under reflux in 250 ccs. oi acetone for 12 hours. The clear acetone solution is concentrated and after cooling the precipitated condensation product is filtered I with suction, washed with acetone and ether' and dried at 100 C. 25.5 grams melting at 182 C. are obtained.

The same product may be obtained when boiling under reflux 12.4 grams of 4.4'-diamino-di-phenylsulphone and l-isocyanate-benzene 3.5-dicarboxylic acid methyiester (melting at 107 0., obtained from 1-aminobenzene-3.S-dhcarboxylic arated in crystals is filtered with suction, washed with ether and dried at 100 C. 39 grams melting 19 grams of this condensation product are suspended in 150 cos. of glacial acetic acid and 50 ccs. of hydrogen peroxide are added. While stirring'the product gradually dissolves. The crystalline precipitate obtained after 16 hours further stirring is filtered with suction washed with water and dried at 100 C. It melts at 206- 207" C. V

The same product is obtained when boiling under refiux 24.8 grams of 4.4'-diaminodiphenylsulphone and 25.8 grams of isocyanato-acetie acid methylester-hydrochloride and phosgene in ortho-dichlorobenzene at I'm-180 C.) in 250 ccs. of acetone for 12 hours. The clear acetone solution is concentrated and the precipitated condensation product is filtered with suction, washed with acetone and ether and dried at 100 C. 32

grams melting at 180-181 C. (with decomposi- Emmple 14 1'1 grams oi. bis-[N-(3'-cyanphenyi)-carbamido-N -phenyl-4l-sulphone are saponified with alcoholic sodium hydroxide solution (10%) tered with suction, washed with ether and dried at 100 C. 1'I.5 grams of the condensation prod- C. (with decomposition) are obtained.

Example 15' 49.5 grams of bis- [N'-carbomethoxymethylcarbamido-N-phenyl-4l-sulphone are suspended in dilute sodium hydroxide solution (10%). The solution is stirred for 10 minutes at C. .The yellowish colored clear solution is acidified with dilute'hydrochloric acid and the dicarboxylic acidv formed is precipitated as an amorphous powder. 35.5 grams melting at 197 C. are obtained after filtering with suction,-washing with water and drying at 100 C.

The starting material is prepared in the following manner:

ester in 250 ccs. of acetone for 4 hours. The acetone solution is concentrated. The condensation product which has separated in crystals is filtered with suction, washed with ether and dried at 100 C. 49.5 grams melting at 207- 208 C. (with decomposition) are obtained.

The same product is obtained when boiling 7 under reflux 23.2 grams of 4.4'-diaminodiphenylsulphoxide and 26 grams of isocyanato-acetic ester in 250 ccs. of acetone i'or4 hours. The acetone solution is concentrated and the condensation product which has separated in crystals is sucked on, washed with ether and dried at 100 C. 49 grams are obtained, melting at 200 C.

The corresponding sulphone compound melting at 207-208 C. is obtained herefrom by treatment with hydrogen peroxide in glacial acetic acid solution.

Example 16 28 grams of bis- [N'-carbomethoxymethylcarbamido-N-phenyl-2 methyl-4]-sulphone are suspended in dilute sodium hydroxide solution (10%). The mixture isstirred at 50 C. for 10 minutes, acidified and the dicarboxylic acid is precipitated as an amorphous powder. 24 grams melting at 198C. are obtained after sucking oif, washing with water and drying at 100 C.

The starting material is prepared in the" following manner: 14.5 grams of 4.4'-diamino- 2.2-diinethyl-diphenyl-sulphone and 13.6 grams ration'of the acetone the condensation product 21.6 grams of 4.4'-diaminodiphenylsulphide and 26 grams of isocyanato-acetic ester are'boiled under reflux in 250 ccs. of acetone for 2 hours.

The condensation product formed which has sepprecipitates. 28 grams melting at 208-210 C. are obtained after sucking oil, washing with ether and drying at C.

Example 17' 40 grams of bis-[N'-(2-chloro-5f-phenylsulphonic acid phenylester) -carbamido-N-phenyl- 4l-sulphone are saponified by short boiling with alcoholic sodium hydroxide solution (10%). 30 grams of disodium salt of the corresponding disulphonic acid crystallize out in the cold.

The starting material is obtained in the following manner: 7

15 grams of diphenylsulphone-4.4'-di-isocy anate and 28.4 grams 4-chloro-3-aminobenzenesulphonic acid phenylester in 200 ccs. of acetone are boiled under reflux for 6 hours. The. acetone solution is concentrated and stirred with water, whereupon the condensation product precipitates'in the beginning as a semisolid sub stance which after a prolonged storing solidifies.

The 4-chloro-3-amino-benzenesulphonic acid phenylester is prepared by reducing grams of 2-nitro-1-cl'llorobenzene-4-sulphonic acid phenylester (from the correspondingsulphochloride and sodium phenolate, melting at '72? C.) with too grams'oi' iron in 1000 cos. of water of chlorosulphonicacid while stirring, whereupon -the temperature rises to 40 C. After 3 hours stirring'at-80 C. the reaction solution is poured on-to ice, the precipitate is sucked ofi. washed with water and well pressed on. The reaction product, probably having the constitution o! 'a bis-[N'-4'-sulphochloridep enyl)- carbamido-N-phenyl-4] -sulphone, is dissolv by gentle heatingwith dilute sodium hydroxide solution (10%), and the disodium salt oi' the bis- [N' (4' phenylsulphonic acid) carbamido- N-phenyl-4l -su1phone is salted out with sodium chloride; v 1 I The starting material is prepared in the 01- lowing manner:

and 23.8 grams oi phenylisocyanate are boiled under reflux in 250 ccs. of acetone ior 4 hours.

The acetone solution is concentrated and the crystallized condensation product is sucked oil, washed with ether and dried at 100 C. 36 grams melting at 250-251 C. (with'decomposition) are obtained.

Example 19 17.3 grams of aniline-2-sulphonic acid aredis- I I I 110 grams of 2-amino-1-chlorobenaene-4-sulphonic acid phen-- unusual-mattress, 1mm zai grams oi potassium-i-naphthylamineJ-sul diphenylsulphone-tf-f phonate and 15 oi diisocyana I I.

tram e z;

r 18.8 :mm e1 '1'.3-phenylenediamin'e-4-sul-' phonic-acid. are dissolved in"50ccs. oi Z-normalsodium hydroxide solution and 100 cos. of water.

A solution citoi'- diphenylstflphOii0-4.4' di-isocyanate in 1.50 cos. of acetone are added drop by dropat ordinarytemperature while ring. The temperature rises from 2011p to 3030,

'A iter 5 hoursstirring the solutionis filtration trom some undissolvedsubstance prosfiltrate.

acid.

Example 22 "65 grams oi 2'-naphthylamine-3.6-disulphonic- I acid (mono-sodium salt) are dissolved 111.5100

I Y '25 24.8 grams of 4. 4'-diaminodiphenylsulphone cos. of ii -normai sodiuinhydroxide solution and 250 cos. ofwater. A. solution of 30 of diphenylsulphone-4.4'-dl-isocyanate in 250 of. acetone are added drop by drop while stirring at 55 C. and subsequently stirred tor 4 hours-at I 65 c. The acetone is evaporated; the aqueous solution filtered whilehot and the filtrate diluted. with 1000ccs. of 0.35% sodium chloride solu-.

' 'tion. The his [N' (3'.6'-naphthalene-disul-.

solved in 50 ccs. of 2-normal sodium hydroxide I solution and 100 cos. of water. A solution 0115 grams of diphenylsulphone-4.4'-di-isocyanate in 150 cos. of acetone is added drop by drop while stirring at 45 C. After 1 hour's stirring at 45-50'C. the reaction solution is filtered and the acetone evaporated. The remaining aqueous solution (200 ccs.) is poured into 800 ccs. oi a Y chloride solution while stirring.

In an analogous manner 25' grams oi the disodium salt of the bis-.[N-( 3'-phenyl-sulphonic acid) -carbamido-N-phenyl-4l-sulphone are obtained from 17.3 grams oi"aniline-3 -sulphonic acid and 15 grams of diphenylsulphone-4.4'-diisocyanate.

Example 20 24.5 grams of sodium-1-naphthylamine-6- sulphonate are dissolved in 150 ccs. of water. A solution of 15 grams of diphenylsulphone-4.4'- di-isocyanate in 150 ccs. of acetone is added drop by drop while stirring at C. After 3 hours stirring at C. the solution is filtered while hot and the acetone evaporated from the filtrate. The remaining aqueous solution (265 ccs.) is poured into 800 ccs. 01' a 35% sodiumchloride solution while stirring. whereupon. the disodium salt of the bis-[Nf-(W-naphthalenesulphonic acid) carbamido N phenyi 4]- sulphone probably formed precipitates. The yield amounts to 35 grams.

'315 grams of the dipotassium salt of the bis- [!i'-(8'-naphthaiene sulphonic acid) -carbamidophonic acid 2 -carbanrido-N-phenyl-4]-sulphone probably formed precipitates after 'addition of a small quantity oiconcentrated hyd'ro-. chloric acid, it is sucked oi! and dried at C. 78 grams obtained which are readily soluble in warm water. I

I Example 23 19 grams oi" .z-nsphthylamino-fi-carboniic acid are dissolved, in 50 of 2-normal sodium hydroxide solution and 200 cos. of water and. 15 grams 0'1 diphenylsulphone-4.4'-di-isocyanate in 250 ccs. of acetone are added drop by drop while stirring at 55 C. After 3 hours stirring the acetone .is evaporated, the aqueous ,solution is filtered and the filtrate poured into 1000 cos. 0!.

a 35% sodiumchloride solution while stirring; The .bis-[N' (6' carbox'y-naphthyl-2')carbamido-N-phenyl-4l-sulphone probably formed precipitates, is suckedofl and dried at 100 C. The yield amounts to'30 grams.

Example 24 34.7 grams of sodium-2-naphthylamino-4.8- disulphonate are dissolved in 150. ccs. of water and an acetone solution of 15 grams or diphenylsulphone-4.4'-di-iso-cyanate in 100 ccs. oi acetone is added drop by drop while stirring at 50 C. After 3 hours stirring at 60 C..the acetone is evaporated, the remaining aqueous solution is filtered and the filtrate is poured into 900 ccs. or 35% sodiumchloride solution while stirring. The bis-[N'-(4'.3-naphthalene-disulphonic acid 2) carbamido-N-phenyl fl-sulphone probably formed precipitates. is sucked oil and dried at 100 C. The yield amounts to 31 grams. The product is soluble in water.

In an analogous manner 22 grams 0! a condensation' product. probably corresponding to the bis-[N' (6'.8' naphthalene-disulphonic acid- 2')-carbamido-N phenyl-4]rsulphone, are obtained from 32.5 grams of the mono-sodium salt ent. and the acetone is evaporated 18 grams oi -bis-tN'-3'-aminophenyl-'- 4'-sulphonic acid) -carbamido-N-phenyl-4l .-iul= phoneare precipitated-tram the remaining aqueous solution by concentrated hydrochloric di-isocyanate of the 2-naphthylamine-6.8-disulphonic acid and 15 grams of diphenylsulphone-4.4'-di-isocyanate.

Example 25 49 grams oi sodium-2-naphthylamine-8-sulphonate are dissolved in 350 cos. of water. A solution or 30 grams oi di-phenylsulphone-4.4'-

in 250 ccs. oi acetone is added drop by'drop while stirring at 55-80' C. Jitter a subsequent ihours stirring at 60-65 C. the

amido-N-phenyl-il-sulphone (30 grams) are obtained from 15 grams of diphensylsulphone- 4.4'-.di-isocyanate and 24.5 grams oi sodium-2- naphthylamine-B-sulphonate, 22.3 grams of 2- naphthylamine-S-sulphonic acid, 24.5 grams of sodium-2-naphthylamine-7-sulphonate respec-.

tively.

We claim:

l. Bis -(para carbamido aryl) q sulphones in which the aryl radical is a benzene radical and in which the nitrogen atoms of the carbamide groups not linked with the aryl radicals are each mono-substituted by a radical rendering the products soluble in water which radical is selected from the group consisting of the radicals of aliphatic polyhydroxy compounds deri ed from sugars and or lower alkyl carboxylic and sulphonic acids and aromatic carboxylic, sulphonic and sulphinic acids of benzene and naphthalene, said products, in so tar as they contain an acid group in the form of their alkali and alkaline earth metal-, ammoniumand amine-salts, are soluble in water with neutral reaction.

2. The products of the iormula wherein R and R1 stand for a radical renderin the products soluble in water which radical is selected from the group consisting of the radicals of aliphatic polyhydroiw compounds derived from sugars and or lower alkyl carboxylic and sulphonic acids and aromatic carboxylic, sulphonic and sulphinic acids of benzene and naphthalene. said products, in so far as they contain an acid group in the term of their alkali and alkaline earthmetal-, ammoniumand amine-salts, are soluble in water with neutral reaction.

C. The yield tral reaction.

sodium chloride j 3. Bis -(para carbamido aryl) sulphones in which the aryl radical is a benzene radical and in which the nitrogen atoms 01' the carbamide groups not linked with the aryl radicals are each mono-substituted by a naphthalene sulphonic acid radical, which products are in the form of their alkali and alkaline earth metal-, ammoniumand amine-salts soluble in water with neu- 4. Theproducts oi the formula a-Nn-o o-nNO-BorONn-c o-manl wherein R and R1 stand for a naphthalene sulphonic acid radical, which products are in the form or their alkali and alkaline earth metal-, ammoniumand amine-salts soluble in water with neutral reaction.

5. The products or the formula- ZO-mroonri so. I

wherein-X and x stand for asulphonic acid group and n stands for one of the numbers 1. 2 and 8, which products are in they form of their alkali and alkaline earth metal-, ammoniumand amine-salts soluble in water with neutral re.

action. c

6. The process which comprises reacting upona di-phenylsulphone-4.4'-di-isocyanate with a primary organic amine the organic radical of which amine is selected from the group consisting 01' the radicals of aliphatic polyhydroxy compounds derived from sugars and of lower alkyl carboxylic and sulphonic acids and aromatic caraminonaphthalene sulphonate.

10. The process which comprises reacting upon a di-phenylsulphone-iAK-di-ismyanate with an aminonaphthalene alkali metal sulphonate.

PAUL P6818. FRITZ MIETZSCH.

Disclaimr 2,297,024.Paul Pdlds and Fritz Mietzsch, WuppertaLElberfeld, German Dumm- SULPHONE DERIVATIVES. Patent dated Sept. 29, 1942. Disc aimer filed Aug. 27, 1949, by the assignee, Winthrop-Steam Inc. Hereb enters this disclaimer to claim 7 of said patent.

[03W Gazette October 4, 1949.1 

